Fungicidal combinations

ABSTRACT

The invention relates to a method of combating phytopathogenic diseases on crop plants which comprises applying to the crop plants or the locus thereof being infested with said phytopathogenic disease an effective amount of a combination of 
     a) a benzophenone of formula I                    
      wherein R 1  is methoxy or methyl, R 2  is C 1 -C 4 alkoxy or 2-halogenbenzyloxy, R 3  is C 1 -C 4 alkoxy, R 4  is C 1 -C 4 alkyl, halogen or trifluoromethyl, and R 5  is hydrogen, halogen, C 1 -C 4 alkoxy, trifluoromethyl or nitro; 
     in association with 
     b) a compound selected from the group comprising compounds of formulae II, III, IV, V, VI, VII, VIII, IX, X and XI as described herein.

“This application is a continuation of International Application No.PCT/EP00/05433, filed Jun. 13, 2000, the contents of which areincorporated herein by reference.”

The present invention relates to novel fungicidal compositions for thetreatment of phytopathogenic diseases of crop plants, especiallyphytopathogenic fungi, and to a method of combating phytopathogenicdiseases on crop plants.

It is known that certain substituted benzophenone derivatives havebiological activity with high systemicity against phytopathogenic fungi,e.g. known from EP-A-897904 and EP-A-899255 where their properties andmethods of preparation are described. On the other hand certainstrobilurin derivatives, cyanoimidazole and carbonic acid amidecompounds are known from the literature as plant fungicides forapplication in various crops of cultivated plants. However, croptolerance and activity against phytopathogenic plant fungi of the knowncompounds do not always satisfy the needs of agricultural practice inmany incidents and aspects.

It has now been found that the use of

a) a benzophenone of formula I

 wherein

R₁ is methoxy or methyl,

R₂ is C₁-C₄alkoxy or 2-halogenbenzyloxy,

R₃ is C₁-C₄alkoxy,

R₄ is C₁-C₄alkyl, halogen or trifluoromethyl, and

R₅ is hydrogen, halogen, C₁-C₄alkoxy, trifluoromethyl or nitro; inassociation with

b) the strobilurin of formula II

is particularly effective in combating or preventing fungal diseases ofcrop plants. These combinations exhibit synergistic fungicidal activity.

The compounds of formula I are known from EP-A-897904 and EP-A-899255.Specific examples of preferred individual compounds are listed in thefollowing table.

No. R₁ R₂ R₃ R₄ R₅ I.01 OCH₃ OCH₃ OCH₃ CH₃ Br I.02 OCH₃ OCH₃ OCH₃ CH₃ ClI.03 OCH₃ OC₂H₅ OCH₃ CH₃ Cl I.04 OCH₃ OC₃H₇-n OCH₃ CH₃ Cl I.05 OCH₃ OCH₃OCH₃ CH₃ CF₃ I.06 OCH₃ OCH₃ OCH₃ Cl H I.07 OCH₃ OCH₃ OCH₃ CF₃ H I.08OCH₃ OCH₃ OCH₃ CH₃ H I.09 OCH₃ OCH₃ OCH₃ Cl Br I.10 OCH₃ OCH₃ OCH₃ ClCH₃ I.11 CH₃ OCH₃ OCH₃ CH₃ Cl I.12 CH₃ OCH₃ OCH₃ CH₃ Br I.13 CH₃ OCH₃OCH₃ CH₃ NO₂ I.14 CH₃ OCH₃ OCH₃ CH₃ OCH₃ I.15 CH₃ OCH₃ OC₄H₉-n CH₃ ClI.16 CH₃ OCH₃ OC₄H₉-n CH₃ Br I.17 CH₃ OCH₃ OC₄H₉-n CH₃ NO₂ I.18 CH₃ OCH₃OC₄H₉-n CH₃ OCH₃ I.19 CH₃ —OCH₂-2-F—C₆H₄ OC₄H₉-n CH₃ Cl I.20 CH₃—OCH₂-2-F—C₆H₄ OC₄H₉-n CH₃ Br I.21 CH₃ —OCH₂-2-F—C₆H₄ OC₄H₉-n CH₃ NO₂I.22 CH₃ —OCH₂-2-F—C₆H₄ OC₄H₉-n CH₃ OCH₃

The chemical designation of the above listed compounds is as follows:

1.01 5-bromo-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone,

1.02 5-chloro-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone,

1.03 5-chloro-6,6′-dimethyl-3′-ethoxy-2,2′,4′-trimethoxy-benzophenone,

1.04 5-chloro-6,6′-dimethyl-3′-propoxy-2,2′,4′-trimethoxy-benzophenone,

1.055-trifluoromethyl-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone,

1.06 6-chloro-6′-methyl-2,2′,3′,4′-tetramethoxy-benzophenone,

1.07 6-trifluoromethyl-6′-methyl-2,2′,3′,4′-tetramethoxy-benzophenone,

1.08 6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone,

1.09 5-bromo-6-chloro-6′-methyl-2,2′,3′,4′-tetramethoxy-benzophenone,

1.10 6-chloro-5,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone,

1.11 5-chloro-2,6,6′-trimethyl-2′,3′,4′-trimethoxy-benzophenone,

1.12 5-bromo-2,6,6′-trimethyl-2′,3′,4′-trimethoxy-benzophenone,

1.13 5-nitro-2,6,6′-trimethyl-2′,3′,4′-trimethoxy-benzophenone,

1.14 2,6,6′-trimethyl-5,2′,3′,4′-tetramethoxy-benzophenone,

1.15 5-chloro-2,6,6′-trimethyl-2′-butoxy-3′,4′-dimethoxy-benzophenone,

1.16 5-bromo-2,6,6′-trimethyl-2′-butoxy-3′,4′-dimethoxy-benzophenone,

1.17 5-nitro-2,6,6′-trimethyl-2′-butoxy-3′,4′-dimethoxy-benzophenone,

1.18 2,6,6′-trimethyl-2′-butoxy-5,3′,4′-trimethoxy-benzophenone,

1.195-chloro-2,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-3′,4′-dimethoxy-benzophenone,

1.205-bromo-2,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-3′,4′-dimethoxy-benzophenone,

1.215-nitro-2,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-3′,4′-dimethoxy-benzophenone,and

1.222,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-5,3′,4′-trimethoxy-benzophenone.

The compound of formula II is known from the literature under commonname picoxystrobin, code ZNC 90160, e.g. from EP-A-278595.

The compound of formula III is known from the literature under code BAS50001F, e.g. from WO 96/01256.

The compound of formula IV is known from the literature, e.g. from WO96/36615.

The compound of formula V is known from the literature, e.g. from WO95/04728.

The compound of formula VI is known from the literature under code IKF916, e.g. from EP-A-705823.

The compound of formula VII is known from the literature under commonname iprovalicarb, code SZX 722, e.g. EP-A-398072.

The compound of formula VIII is known from the literature under commonname fenamidone, code RPA 407213, e.g. from EP-A-629616.

The compounds of formula IX are known from the literature, e.g. from WO96/04252.

The compound of formula X is known from the literature under code RH7281, e.g. from EP-A-600629.

The compound of formula XI is known from the literature under commonname fenhexamide, code KBR 2738, e.g. from EP-A-339418.

Specifically, the combinations of this invention comprise

1) 5-bromo-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone (compound1.01) in combination with any of the compounds II, III, IV, V, VI, VII,VIII, IX, X or XI,

2) 5-chloro-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone (compound1.02) in combination with any of the compounds II, III, IV, V, VI, VII,VIII, IX, X or XI,

3) 5-chloro-6,6′-dimethyl-3′-ethoxy-2,2′,4′-trimethoxy-benzophenone(compound 1.03) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

4) 5-chloro-6,6′-dimethyl-3′-propoxy-2,2′,4′-trimethoxy-benzophenone(compound 1.04) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

5) 5-trifluoromethyl-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone(compound 1.05) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

6) 6-chloro-6′-methyl-2,2′,3′,4′-tetramethoxy-benzophenone (compound1.06) in combination with any of the compounds II, III, IV, V, VI, VII,VIII, IX, X or XI,

7) 6-trifluoromethyl-6′-methyl-2,2′,3′,4′-tetramethoxy-benzophenone(compound 1.07) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

8) 6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone (compound 1.08) incombination with any of the compounds II, III, IV, V, VI, VII, VIII, IX,X or XI,

9) 5-bromo-6-chloro-6′-methyl-2,2′,3′,4′-tetramethoxy-benzophenone(compound 1.09) in combination with any of the compounds II, III, IV, V,VI, VIII, VIII, IX, X or XI,

10) 6-chloro-5,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone(compound 1.10) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

11) 5-chloro-2,6,6′-trimethyl-2′,3′,4′-trimethoxy-benzophenone (compound1.11) in combination with any of the compounds II, III, IV, V, VI, VII,VIII, IX, X or XI,

12) 5-bromo-2,6,6′-trimethyl-2′,3′,4′-trimethoxy-benzophenone (compound1.12) in combination with any of the compounds II, III, IV, V, VI, VII,VIII, IX, X or XI,

13) 5-nitro-2,6,6′-trimethyl-2′,3′,4′-trimethoxy-benzophenone (compound1.13) in combination with any of the compounds II, III, IV, V, VI, VII,VIII, IX, X or XI,

14) 2,6,6′-trimethyl-5,2′,3′,4′-tetramethoxy-benzophenone (compound1.14) in combination with any of the compounds II, III, IV, V, VI, VII,VIII, IX, X or XI,

15) 5-chloro-2,6,6′-trimethyl-2′-butoxy-3′,4′-dimethoxy-benzophenone(compound 1.15) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

16) 5-bromo-2,6,6′-trimethyl-2′-butoxy-3′,4′-dimethoxy-benzophenone(compound 1.16) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

17) 5-nitro-2,6,6′-trimethyl-2′-butoxy-3′,4′-dimethoxy-benzophenone(compound 1.17) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

18) 2,6,6′-trimethyl-2′-butoxy-5,3′,4′-trimethoxy-benzophenone (compound1.18) in combination with any of the compounds II, III, IV, V, VI, VII,VIII, IX, X or XI,

19)5-chloro-2,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-3′,4′-dimethoxy-benzophenone(compound 1.19) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

20)5-bromo-2,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-3′,4′-dimethoxy-benzophenone(compound 1.20) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI,

21)5-nitro-2,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-3′,4′-dimethoxy-benzophenone(compound 1.21) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI, and

22)2,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-5,3′,4′-trimethoxy-benzophenone(compound 1.22) in combination with any of the compounds II, III, IV, V,VI, VII, VIII, IX, X or XI

Among these preferred mixtures are those of the compounds of formula Iwith the compounds of formulae II, III, IV, V, X and XI, with even morepreference to compounds II, III, X and XI.

Throughout this document the expression combination stands for thevarious combinations of components a) and b), e.g. in a single“ready-mix” form, in a combined spray mixture composed from separateformulations of the single active ingredient components, e.g. a“tank-mix”, and in a combined use of the single active ingredients whenapplied in a sequential manner, i.e. one after the other with areasonably short period, e.g. a few hours or days. The order of applyingthe components a) and b) is not essential for working the presentinvention.

The combinations according to the invention may also comprise more thanone of the active components b), if broadening of the spectrum ofdisease control is desired. For instance, it may be advantageous in theagricultural practice to combine two or three components b) with the anyof the compounds of formula I, or with any preferred member of the groupof compounds of formula I.

The active ingredient combinations are effective against phytopathogenicfungi belonging to the following classes: Ascomycetes (e.g. Venturia,Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula);Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia, Puccinia); Fungiimperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium,Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporellaherpotrichoides); Oomycetes (e.g. Phytophthora, Peronospora, Bremia,Pythium, Plasmopara).

Target crops for the areas of indication disclosed herein comprisewithin the scope of this invention e.g. the following species of plants:cereals (wheat, barley, rye, oats, rice, sorghum and related crops);beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit(apples, pears, plums, peaches, almonds, cherries, strawberries,raspberries and blackberries); leguminous plants (beans, lentils, peas,soybeans); oil plants (rape, mustard, poppy, olives, sunflowers,coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants(marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute);citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables(spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes,potatoes, paprika); lauraceae (avocados, cinnamon, camphor); or plantssuch as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops,turf, bananas and natural rubber plants, as well as ornamentals(flowers, shrubs, broad-leaved trees and evergreens, such as conifers).This list does not represent any limitation.

The combinations of the present invention may also be used in the areaof protecting technical material against attack of fungi. Technicalareas include wood, paper, leather, constructions, cooling and heatingsystems, ventilation and air conditioning systems, and the like. Thecombinations according the present invention can prevent thedisadvantageous effects such as decay, discoloration or mold.

The combinations according to the present invention are particularlyeffective against powdery mildews and rusts, pyrenophora,rhynchosporium, tapesia, fusarium and leptosphaeria fungi, in particularagainst pathogens of monocotyledonous plants such as cereals, includingwheat and barley. They are furthermore particularly effective againstdowny mildew species, powdery mildews, leaf spot diseases and rusts indicotyledonous plants.

The amount of combination of the invention to be applied, will depend onvarious factors such as the compound employed, the subject of thetreatment (plant, soil, seed), the type of treatment (e.g. spraying,dusting, seed dressing), the purpose of the treatment (prophylactic ortherapeutic), the type of fungi to be treated and the application time.

It has been found that the use of compounds of formula II in combinationwith the compound of formula I surprisingly and substantially enhancethe effectiveness of the latter against fungi, and vice versa.Additionally, the method of the invention is effective against a widerspectrum of such fungi that can be combated with the active ingredientsof this method, when used solely.

The weight ratio of a):b) is so selected as to give a synergisticfungicidal action. In general the weight ratio of a): b) is between200:1 and 1:40. The synergistic action of the composition is apparentfrom the fact that the fungicidal action of the composition of a)+b) isgreater than the sum of the fungicidal actions of a) and b).

Where the component b) is the compound of formula II the weight ratio ofa):b) is for example between 40:1 and 1:60, especially 20:1 and 1:60.Where the component b) is the compound of formula III the weight ratioof a):b) is for example between 10:1 and 1:20, especially 8:1 and 1:15,and more preferably 5:1 and 1:10. Where the component b) is the compoundof formula IV the weight ratio of a):b) is for example between 40:1 and1:15, especially 20:1 and 1:10, and more preferably 10:1 and 1:2. Wherethe component b) is the compound of formula V the weight ratio of a):b)is for example between 40:1 and 1:60, especially 20:1 and 1:60. Wherethe component b) is the compound of formula VI the weight ratio of a):b)is for example between 40:1 and 1:10, especially 20:1 and 1:8, and morepreferably 10:1 and 1:5. Where the component b) is the compound offormula VII the weight ratio of a):b) is for example between 10:1 and1:5, especially 7:1 and 1:5, and more preferably 2:1 and 1:2. Where thecomponent b) is the compound of formula VIII the weight ratio of a):b)is for example between 40:1 and 1:15, especially 20:1 and 1:10, and morepreferably 10:1 and 1:2. Where the component b) is the compound offormula IX the weight ratio of a):b) is for example between 15:1 and1:25, especially 10:1 and 1:20, and more preferably 5:1 and 1:10. Wherethe component b) is the compound of formula X the weight ratio of a):b)is for example between 200:1 and 1:10, especially 100:1 and 1:8, andmore preferably 50:1 and 1:1. Where the component b) is the compound offormula XI the weight ratio of a):b) is for example between 5:1 and1:50, especially 2:1 and 1:40, and more preferably 1:1 and 1:20.

The method of the invention comprises applying to the treated plants orthe locus thereof in admixture or separately, a fungicidally effectiveaggregate amount of a compound of formula I and a compound of componentb).

The term locus as used herein is intended to embrace the fields on whichthe treated crop plants are growing, or where the seeds of cultivatedplants are sown, or the place where the seed will be placed into thesoil. The term seed is intended to embrace plant propagating materialsuch as cuttings, seedlings, seeds, germinated or soaked seeds.

The novel combinations are extremely effective on a broad spectrum ofphytopathogenic fungi. Some of them have a systemic action and can beused as foliar and soil fungicides and for seed dressing.

The fungicidal combinations are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, maize, lawns, cotton, soybeans, coffee,sugarcane, fruit and ornamentals in horticulture and viticulture, invegetables such as cucumbers, beans and cucurbits, and in field cropssuch as potatoes, peanuts, tobacco and sugarbeets.

The combinations are applied by treating the fungi or the seeds, plantsor materials threatened by fungus attack, or the soil with afungicidally effective amount of the active ingredients.

The agents may be applied before or after infection of the materials,plants or seeds by the fungi.

The novel combinations are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton, potatoes, rice and lawns,

Ustilago species in cereals and sugarcane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Septoria tritici in wheat,

Rhynchosporium secalis on barley,

Botrytis cinerea (gray mold) in strawberries, tomatoes and grapes,

Cercospora arachidicola in groundnuts,

Peronospora tabacina in tobacco, or other Peronospora in various crops,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyrenophera teres in barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables,

Pseudoperonospora cubensis in cucumbers,

Mycosphaerella fijiensis in banana,

Colleotrichum species in various crops.

When applied to the plants the compounds of formula I are applied at arate of 20 to 2000 g/ha, particularly 20 to 1000 g/ha, e.g. 20, 30, 40,75, 80, 100, 125,150, 175, 200, 300, 500, 750, 1000,1200,1500 or 2000g/ha, in association with 10 to 750 g/ha, particularly 20 to 1000 g/ha,e.g. 12.5 g/ha, 15 g/ha, 30 g/ha, 40 g/ha, 60 g/ha, 75 g/ha, 80 /ha, 100g/ha, 125 g/ha, 150 g/ha, 175 g/ha, 200 g/ha, 250 g/ha, 300 g/ha, 500g/ha, 600 g/ha or 750 g/ha of a compound of component b).

Where the component b) is the compound of formula II for example 50 to300 g a.i./ha is applied in association with the compounds of formula I.Where the component b) is the compound of formula III for example 250 to350 g a.i./ha is applied in association with the compounds of formula I.Where the component b) is the compound of formula IV for example 50 to300 g a.i./ha is applied in association with the compounds of formula I.Where the component b) is the compound of formula V for example 50 to300 g a.i./ha is applied in association with the compounds of formula I.Where the component b) is the compound of formula VI for example 50 to150 g a.i./ha is applied in association with the compounds of formula I.Where the component b) is the compound of formula VII for example 100 to300 g a.i./ha is applied in association with the compounds of formula I.Where the component b) is the compound of formula VIII for example 50 to300 g a.i./ha is applied in association with the compounds of formula I.Where the component b) is the compound of formula IX for example 150 to500 g a.i./ha is applied in association with the compounds of formula I.Where the component b) is the compound of formula X for example 10 to200 g a.i./ha is applied in association with the compounds of formula I.Where the component b) is the compound of formula XI for example 500 to1000 g a.i./ha is applied in association with the compounds of formulaI.

In agricultural practice the application rates of the combination dependon the type of effect desired, and range from 0.02 to 3 kg of activeingredient per hectare.

When the active ingredients are used for treating seed, rates of 0.001to 50 g a.i. per kg, and preferably from 0.01 to 10 g per kg of seed aregenerally sufficient.

The invention also provides fungicidal compositions comprising acompound of formula I and a compound of component b).

The composition of the invention may be employed in any conventionalform, for example in the form of a twin pack, an instant granulate, aflowable formulation, an emulsion concentrate or a wettable powder incombination with agriculturally acceptable adjuvants. Such compositionsmay be produced in conventional manner, e.g. by mixing the activeingredients with appropriate adjuvants (diluents or solvents andoptionally other formulating ingredients such as surfactants). Alsoconventional slow release formulations may be employed where longlasting efficacy is intended.

Particularly formulations to be applied in spraying forms such as waterdispersible concentrates or wettable powders may contain surfactantssuch as wetting and dispersing agents, e.g. the condensation product offormaldehyde with naphthalene sulphonate, an alkylarylsulphonate, alignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenoland an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to theseeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g. as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant and 10to 99.99% solid or liquid adjuvant(s), the active agent consisting of atleast the compound of formula I together with a compound of componentb), and optionally other active agents, particularly microbides orconservatives or the like. Concentrated forms of compositions generallycontain in between about 2 and 80%, preferably between about 5 and 70%by weight of active agent. Application forms of formulation may forexample contain from 0.01 to 20% by weight, preferably from 0.01 to 5%by weight of active agent. Whereas commercial products will preferablybe formulated as concentrates, the end user will normally employ diluteformulations.

The Examples which follow serve to illustrate the invention, “activeingredient” denoting a mixture of compound I and a compound of componentb) in a specific mixing ratio.

FORMULATION EXAMPLES

Wettable powders a) b) c) active ingredient [comp a:comp b) = 25%  50% 75% 1:3(a), 1:2(b), 1:1(c)] sodium lignosulfonate 5% 5% — sodium laurylsulfate 3% —  5% sodium diisobutylnaphthalenesulfonate — 6% 10% phenolpolyethylene glycol ether — 2% — (7-8 mol of ethylene oxide) highlydispersed silicic acid 5% 10%  10% kaolin 62%  27% 

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

Emulsifiable concentrate active ingredient (comp a:comp b) = 1:6) 10%octylphenol polyethylene glycol ether  3% (4-5 mol of ethylene oxide)calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether (35 molof ethylene oxide)  4% cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) active ingredient [comp a:comp b) = 1:6(a),  5%  6%  4%1:2(b), 1:10(c)] talcum 95% — — kaolin — 94% — mineral filler — — 96%

Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier and grinding the mixture in a suitable mill. Such powderscan also be used for dry dressings for seed.

Extruder granules active ingredient (comp a:comp b) = 2:1) 15% sodiumlignosulfonate  2% carboxymethylcellulose  1% kaolin 82%

The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

Coated granules active ingredient (comp a:comp b) = 1:10) 8%polyethylene glycol (mol. wt. 200) 3% kaolin 89% 

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

Suspension concentrate active ingredient (comp a:comp b) = 1:8) 40%propylene glycol 10% nonylphenol polyethylene glycol ether  6% (15 molof ethylene oxide) sodium lignosulfonate 10% carboxymethylcellulose  1%silicone oil (in the form of a 75% emulsion in water)  1% water 32%

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of a combination of the compound of formula I (component a) anda compound of component b), or of each of these compounds separately,are mixed with 2 parts of an aromatic solvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed.

The obtained capsule suspension is stabilized by adding 0.25 parts of athickener and 3 parts of a dispersing agent. The capsule suspensionformulation contains 28% of the active ingredients. The medium capsulediameter is 8-15 microns.

The resulting formulation is applied to seeds as an aqueous suspensionin an apparatus suitable for that purpose.

BIOLOGICAL EXAMPLES

A synergistic effect exists whenever the action of an active ingredientcombination is greater than the sum of the actions of the individualcomponents.

The action to be expected E for a given active ingredient combinationobeys the so-called COLBY formula and can be calculated as follows(COLBY, S. R. “Calculating synergistic and antagonistic responses ofherbicide combination”. Weeds, Vol. 15, pages 20-22; 1967):ppm=milligrams of active ingredient (=a.i.) per liter of spray mixtureX=% action by active ingredient I using p ppm of active ingredient Y=%action by active ingredient II using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredientsI+II using p+q ppm${{of}\quad {active}\quad {ingredient}\quad {is}\quad E} = {X + Y - \frac{X \cdot Y}{100}}$

If the action actually observed (O) is greater than the expected action(E), then the action of the combination is superadditive, i.e. there isa synergistic effect.

Alternatively the synergistic action may also be determined from thedose response curves according to the so-called WADLEY method. With thismethod the efficacy of the a.i. is determined by comparing the degree offungal attack on treated plants with that on untreated, similarlyinoculated and incubated check plants. Each a.i. is tested at 4 to 5concentrations. The dose response curves are used to establish the EC90(i.e. concentration of a.i. providing 90% disease control) of the singlecompounds as well as of the combinations (EC 90_(observed)). The thusexperimentally found values of the mixtures at a given weight ratio arecompared with the values that would have been found were only acomplementary efficacy of the components was present (EC 90(A+B)_(expected)). The EC 90 (A+B)_(expected) is calculated according toWadley (Levi et al., EPPO— Bulletin 16, 1986, 651-657):${{EC}\quad 90\left( {A + B} \right)_{expected}} = \frac{a + b}{\frac{a}{\left( {{EC90}(A)} \right)_{observed}} + \frac{b}{\left( {{EC90}(B)} \right)_{observed}}}$

wherein a and b are the weight ratios of the compounds A and B in themixture and the indexes (A), (B), (A+B) refer to the observed EC 90values of the compounds A, B or the given combination A+B thereof. Theratio EC90 (A+B)_(expected)/EC90 (A+B)_(observed) expresses the factorof interaction (F). In case of synergism, F is >1.

EXAMPLE B-1 Efficacy Against Erysiphe Graminis f.sp. Tritici on Wheat

a) Protective Treatment

Fifteen wheat seeds c.v. “Arina” are sown in plastic pots of 50 ml andgrown for 7 to 12 days at 22/19° C., 50-70% rH in the greenhouse. Whenthe primary leaves have fully expanded, the plants are spray treatedwith aqueous spray liquids containing the single compounds, or mixturesthereof (hereinafter a.i.). All compounds are used as experimental orcommercially available formulations, combinations are applied as tankmixtures. The application comprises foliar spraying to near runoff(three pots per treatment). 7 days after the application, the plants areinoculated in a settling tower with fresh spores of Erysiphe graminis f.sp. tritici by dusting the conidia on the test plants The plants arethen incubated in a growth chamber at 20° C., 60% rH. Six days afterinoculation, the percentage of infection on primary leaves is evaluated.The efficacy of the a.i. is determined by comparing the degree of fungalattack on treated plants with that on untreated, similarly inoculatedand incubated check plants. Each a.i. is tested at 3 to 5concentrations. The results are evaluated according to the COLBY method.

b) Curative Treatment

Wheat plants cv. Arina are grown in standard soil in 50 ml pots (approx.15 plants per pot) in the greenhouse at 22/19° C. and 14 hours light perday. At test begin the plants are 8 days old. For inoculation, conidiaare dusted over the test plants and the plants are incubated at 18-20°C. until treatment. The fungicide treatment is carried out 3 days afterinoculation by spraying the test plants with diluted spray suspensionsof the individual active ingredients or mixtures, being prepared bysuspension in demineralized water and appropriate dilution. 12 plants in3 pots are used for each treatment. 3 to 4 days after treatment thetests are evaluated by estimating the percentage of fungal attack on theleaves. The activity is calculated relative to the disease on the checkplants. The fungicide interactions in the mixtures are calculatedaccording to the COLBY method.

EXAMPLE B-2 Activity Against Uncinula Necator

Grape plants in the 4-6 leaf stage, variety Gutedel, are inoculated withconidia of Uncinula necator by dusting the conidia over the test plants.After 2 days under high humidity and reduced light intensity, the plantsare incubated for 10-14 days in a growth chamber at 70% rH and 22° C. 3days after inoculation the active ingredients and the mixtures areapplied by spraying aqueous suspensions being prepared by suspending thea.i.s in demineralized water and appropriate dilution. 5 plants are usedfor every treatment. 12 days after inoculation the tests are evaluatedby estimating the percentage of fungal leaf attack relative to thedisease on the check plants. The fungicide interactions in the mixturesare calculated according to COLBY method.

The mixtures according to the invention exhibit good activity in themethods of the above Biological Examples 1 and 2.

What is claimed is:
 1. A method of combating phytopathogenic diseases oncrop plants which comprises applying to the crop plants or the locusthereof being infested with said phytopathogenic disease an effectiveamount of a combination of a) a benzophenone of formula I

 wherein R₁ is methoxy or methyl, R₂ is C₁-C₄alkoxy or2-halogenbenzyloxy, R₃ is C₁-C₄alkoxy, R₄ is C₁-C₄alkyl, halogen ortrifluoromethyl, and R₅ is hydrogen, halogen, C₁-C₄alkoxy,trifluoromethyl or nitro; in association with the strobilurin of formulaII


2. A method according to claim 1 wherein the applied amounts of thecomponents a) and b) are so selected as to enhance the fungicidalactivity of each other in a synergistic manner.
 3. A method according toclaim 1 wherein component a) is selected from the group consisting of5-bromo-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone,5-chloro-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone,5-chloro-6,6′-dimethyl-3′-ethoxy-2,2′,4′-trimethoxy-benzophenone,5-chloro-6,6′-dimethyl-3′-propoxy-2,2′,4′-trimethoxy-benzophenone,5-trifluoromethyl-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone,6-chloro-6′-methyl-2,2′,3′,4′-tetramethoxy-benzophenone,6-trifluoromethyl-6′-methyl-2,2′,3′,4′-tetramethoxy-benzophenone,6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone,5-bromo-6-chloro-6′-methyl-2,2′,3′,4′-tetramethoxy-benzophenone,6-chloro-5,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenoe,5-chloro-2,6,6′-trimethyl-2′,3′,4′-trimethoxy-benzophenone,5-bromo-2,6,6′-trimethyl-2′,3′,4′-trimethoxy-benzophenone,5-nitro-2,6,6′-trimethyl-2′,3′,4′-trimethoxy-benzophenone,2,6,6′-trimethyl-5,2′,3′,4′-tetramethoxy-benzophenone,5-chloro-2,6,6′-trimethyl-2′-butoxy-3′,4′-dimethoxy-benzophenone,5-bromo-2,6,6′-trimethyl-2′-butoxy-3′,4′-dimethoxy-benzophenone,5-nitro-2,6,6′-trimethyl-2′-butoxy-3′,4′-dimethoxy-benzophenone,2,6,6′-trimethyl-2′-butoxy-5,3′,4′-trimethoxy-benzophenone,5-bromo-2,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-3′,4′-dimethoxy-benzophenone,2,6,6′-trimethyl-2′-(o-fluorobenzyloxy)-5,3′,4′-trimethoxy-benzophenone.4. A method according to claim 1 wherein the component b) comprises acompound of formulae II, III or IV.
 5. A method according to claim 1wherein component a) is5-bromo-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone and componentb) is a compound of formula II.
 6. A fungicidal composition comprising afungicidally effective combination of components a) and b) according toclaim 1 together with an agriculturally acceptable carrier, andoptionally a surfactant.
 7. A composition according to claim 6 whereinthe ratio of components a) and b) are so selected that the fungicidalactivity is synergistically enhanced.
 8. A composition according toclaim 6 wherein the weight ratio of a) to b) is between 200:1 and 1:40.9. A composition according to claim 6 wherein component a) is5-bromo-6,6′-dimethyl-2,2′,3′,4′-tetramethoxy-benzophenone and componentb) is a compound of formula II.